CN105254469A - Chloroethane clean production process and device - Google Patents
Chloroethane clean production process and device Download PDFInfo
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- CN105254469A CN105254469A CN201510710766.3A CN201510710766A CN105254469A CN 105254469 A CN105254469 A CN 105254469A CN 201510710766 A CN201510710766 A CN 201510710766A CN 105254469 A CN105254469 A CN 105254469A
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Abstract
The invention discloses a chloroethane clean production process and device. The chloroethane clean production process comprises the steps that in a first batch reaction, zinc chloride, ethanol and hydrochloric acid are added into a chloroethane reaction device, and a substitution reaction is conducted at the temperature of 80-120 DEG C; a chloroethane gas mixture coming out of the reaction device is sequentially subjected to first-level cooling, buffering, second-level cooling, first-level water absorption, second-level water absorption, finished product cooling and condensation and segregation of a water segregator, and finished chloroethane is obtained; mixed liquor coming out of the reaction device is subjected to temperature rise and concentration, then a concentrated solution serves as mother liquor and flows back to the chloroethane reaction device for being reused, gas evaporated in the concentration process is subjected to cooling and condensation and then collected, an ethanol solution and a hydrochloric acid solution are recovered from collected liquid through an acid alcohol recovery tower and the collected ethanol solution and the hydrochloric acid solution are reused respectively. According to the chloroethane clear production process and device, a temperature-gradient reaction at the relatively low temperature is adopted, generation of by-products such as diethyl ether can be effectively lowered, and the aftertreatment processes are reduced; by means of a synthetic method, energy consumption can be effectively lowered, production cost can be saved, and clean production and circular economic development requirements are met.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of process for cleanly preparing and device of monochloroethane.
Background technology
At present, halogen alkylation methods is the most frequently used method during monochloroethane is produced, and namely hydrochloric acid and alcohol add in enamel reaction still by a certain percentage and reacts.Steam heating is utilized during reaction, the pressure and temperature of reaction is restricted, the absorption agent such as liquid caustic soda and sulfuric acid also will be used to carry out purification simultaneously, monochloroethane yield is caused to only have about 80%, and the water that the water that unreacted hydrochloric acid, alcohol, raw material are introduced, reaction produce and ether etc. are with monochloroethane in the lump out, last handling process is loaded down with trivial details, and the Waste Sulfuric Acid that produces of scavenging process and waste liquid alkali are because of containing large amount of organic simultaneously, recycle value low, adds somewhat to production cost.
Present domestic manufacturer all adopts halocarbon production method to synthesize monochloroethane, as patent documentation CN102850178A provides a kind of method utilizing gas phase chlorination hydrogen and ethanol to synthesize monochloroethane, it utilizes gas phase chlorination hydrogen and ethanol to synthesize monochloroethane, adopt in reaction and pump into hydrogen chloride gas and the alcohol that mode passes into certain proportioning continuously, 120 DEG C ~ 135 DEG C reactions, although the method decreases hydrochloric acid consumption to a certain extent, decrease wastewater flow rate, but adopt traditional alkali liquid washing and vitriol oil drying in subsequent disposal, product yield must be made to reduce, and produce a large amount of high-salt wastewater and contain organic spent acid.
The increasingly stringent administered along with Environmental and the call of energy-saving and emission-reduction, the halocarbon metallization processes method of monochloroethane is also being updated.Patent documentation CN103044187A discloses this kind of method and system of producing monochloroethane, it adopts special monochloroethane reactor to replace enamel reaction still, 120 DEG C ~ 160 DEG C reactions, separation purifier adopts steel lining tetrafluoro and graphite equipment, ethanol conversion can reach more than 95%, but does not report the further treatment process of monochloroethane gas mixture further in this patent documentation.
For another example patent documentation CN103044188A discloses a kind of halocarbon metallization processes method preparing monochloroethane, it adopts self-control monochloroethane reactor to replace multiple stage reactor, 120 ~ 160 DEG C of reactions, utilize that hydrochloric acid is different with alcohol gaseous phase partial pressure and boiling point substance carries out purification separation, utilize solubleness principle to realize monochloroethane dehydration, the monochloroethane purity obtained is more than 99.5%.But in above technique, all to adopt pyroreaction, follow-up purification needs to adopt rectifier unit, aftertreatment simultaneously still (namely carries out cooling condensation liquefaction by water coolant indirect heat exchange with Alkali absorption in condenser 2, chromatographic separation again, lower floor's ethanol solution hydrochloride that pump (row) goes out chromatography returns special monochloroethane reactor 1 and recycles, chromatography goes out upper strata monochloroethane and adjusts after its pH value reaches 6.0-8.0 through sodium hydroxide solution, drain into monochloroethane work in-process storage tank 3), add aftertreatment cost, and adopt a large amount of hydrochloric acid in reaction, the water yield that raw material is introduced increases, add the energy consumption of mother liquor concentrations.Meanwhile, the sour water of its process is directly discharged as wastewater treatment, adds aftertreatment cost and raw materials consumption.
Summary of the invention
The invention provides a kind of process for cleanly preparing of monochloroethane, by improving technique, realizing whole process non-wastewater discharge, avoiding using alkali liquor absorption and vitriol oil drying simultaneously, reduce the usage quantity of hydrochloric acid and the discharge capacity of acidic and alkaline wastewater, improve the performance of enterprises.
A process for cleanly preparing for monochloroethane, comprises the steps:
(1), in first pot reaction, join in reaction unit by ethanol, zinc chloride and hydrochloric acid, 80 ~ 120 DEG C are carried out substitution reaction;
(2) from reaction unit, monochloroethane gas mixture is out separated obtains finished product monochloroethane through one-level cooling, buffering, one-level cooling, the absorption of one-level water, the absorption of secondary water, finished product cooling condensation, water trap successively; The acid number that described one-level water and secondary water absorb is less than or equal to 25%; When described one-level water absorbs and in the absorption of secondary water, the acid number of water is greater than 20%, change fresh water, hydrogen chloride gas is prepared in the one-level water acid solution simultaneously more swapped out and the reuse of secondary water acid solution, and the assorted pot for step (1) reacts; The liquid that described water trap separates is directly as the absorption Water circulation that one-level water absorbs;
(3) from reaction unit mixed solution out through heat up concentrated after, concentrated solution is back to reuse in the reaction unit of step (1) as mother liquor, the concentrated gas steamed is collected after cooling condensation, the liquid collected reclaims ethanol and hydrochloric acid soln through acid alcohol recovery tower, the ethanol reuse of reclaiming carries out assorted pot reaction to step (1), the reuse of hydrogenchloride body for the preparation of hydrogenchloride body, and is carried out assorted pot reaction to step (1) by the hydrochloric acid soln reclaimed.
As preferably, step (1) adopts temperature-gradient method reaction, is respectively:
First paragraph is warming up to 80 ~ 95 DEG C, reacts 2 ~ 4 hours;
Second segment is warming up to 95 ~ 110 DEG C, and the reaction times is 3 ~ 6 hours;
3rd section is warming up to 110 ~ 120 DEG C, reacts 2 ~ 4 hours.
In first paragraph temperature reaction process, because material concentration is maximum, at relatively low temperature, a part of hydrochloric acid and ethanol can react, and avoiding now heats up causes the hydrogenchloride of high density and ethanol to be escaped; In second segment temperature reaction process, most of hydrogenchloride and ethanol reacted in this stage, and the reaction times is elongated relatively; In 3rd section of temperature reaction process, due to hydrochloric acid in system and alcohol concn relatively low, heat up promote material react completely as far as possible.It can thus be appreciated that, adopt temperature-gradient method reaction, effectively can improve reaction efficiency, reduce the usage quantity of hydrochloric acid; Meanwhile, under avoiding the condition of high temperature, by product particularly ether generates, and improves product yield and purity further.
As preferably, during first pot reaction to be mass percent concentration be 25 ~ 30% hydrochloric acid, wherein in ethanol and hydrochloric acid, the mol ratio of hydrogenchloride is 1:1.15 ~ 1.35.
One-level water of the present invention absorbs and secondary water absorb the absorption liquid after changing can direct reuse, as preferably, the acid number of control one-level water absorption liquid and secondary water absorption liquid is less than or equal to 20%; When one-level water absorption liquid is greater than 15%, secondary water absorption liquid acid number is greater than 5%, change fresh water.As preferred further, hydrogenchloride concentration unit the first order absorption liquid more swapped out and secondary absorption liquid is utilized to synthesize the hydrochloric acid of mass percent concentration 30% or more, utilize this hydrochloric acid to prepare hydrogen chloride gas, directly pass into and carry out assorted pot reaction to step (1).Technical hydrochloric acid mass percent concentration is generally 30%.
In step (2) and (3), the process that assorted pot reaction is carried out in the recovery of hydrochloric acid soln, first order absorption liquid, secondary absorption liquid, ethanol is:
(1) add the ethanol of set amount, described ethanol is selected from the ethanol of ethanol finished product or recovery;
(2) collect hydrochloric acid soln, first order absorption liquid, secondary absorption liquid, the concentrated hydrochloric acid obtained, to hydrogenchloride concentration unit, joins in hydrogen chloride preparation device by reuse, and the hydrogen chloride gas obtained is passed in the mother liquor after reuse again;
(3) after the hydrogen cloride concentration in mother liquor reaches set(ting)value, stop passing into hydrogenchloride; The ethanol added is 1:1.15 ~ 1.25 with the mol ratio of the hydrogenchloride passed into.
As preferably, in step (2):
After one-level cooling, the temperature of monochloroethane gas mixture is 50 ~ 60 DEG C;
After one-level water absorbs, change when acid number is greater than 10%;
After secondary water absorbs, change when acid number is greater than 5%;
After secondary cooling condensation, the temperature of monochloroethane mixture is 20 ~ 40 DEG C;
After finished product cooling condensation, the temperature of monochloroethane mixture is 0 ~ 5 DEG C.
Adopt technique scheme, by absorbing the control of acid number to the absorption of one-level water and secondary water, coordinate one-level cooling, secondary cooling and water separator simultaneously, hydrogenchloride is avoided to enter into final finished, ensure quality product, avoid the disadvantageous effect to subsequent product, the corrosion to e-quipment and pipe can also be reduced simultaneously.In addition, to unreacted ethanol and hydrogenchloride, reclaim comprehensively.
In technique scheme, the acid number of secondary water acid solution is lower, for ease of controlling, can by hydrochloric acid soln Mixed Pinyin needed for secondary water acid solution and preparation of hydrogen chloride, rear reuse is in hydrogen chloride preparation device, or, in secondary absorption liquid reuse to one-level water can being absorbed, after being absorbed by one-level water, reuse is in hydrogen chloride preparation device again, as preferably, in step (2) and (3), during the first reuse of secondary absorption liquid absorbs to one-level water, then obtain changing the hydrochloric acid that first order absorption liquid utilizes hydrogenchloride concentration unit synthesis mass percent concentration 30% or more, to prepare hydrochloric acid joins in hydrogen chloride preparation device, the hydrogen chloride gas obtained is passed in the mother liquor after reuse again and carries out assorted pot reaction.The hydrogenchloride concentration unit that the present invention adopts can adopt existing any device that can realize concentrate function, such as can adopt existing chlor-alkali hydrochloric acid synthetic furnace etc.
Described hydrogen chloride preparation device can adopt existing preparation of hydrogen chloride system, such as, the vitriol oil can be adopted to prepare system.After vitriol oil concentration is reduced to set(ting)value, reuse or be directly used in the synthesis of dispersed dye by dilute sulphuric acid after the sulphuric acid concentration after dilution can being dewatered, specifically describes see patent CN103539700.
Adopt the method, only in first pot reaction, use aqueous hydrochloric acid as raw material, in follow-up reaction, directly can adopt hydrogen chloride gas, reclaim the hydrogenchloride in the aqueous hydrochloric acid and mother liquor finally collected, reduce further usage quantity and the wastewater discharge of hydrogenchloride.When ethanol or hydrogenchloride deficiency, can suitably supplement.
As preferably, the mass percent concentration of zinc chloride controls 55% ~ 75%.
Present invention also offers a kind of cleaning production apparatus of monochloroethane, comprise the monochloroethane reaction unit with opening for feed, gas discharge mouth and liquid outlet opening, also comprise:
The one-level refrigerating unit be connected successively with gas discharge mouth, snubber assembly, secondary refrigerating unit, one-level water absorption unit, secondary water absorption unit, finished product cooling condensation device and water trap, the outlet for product of described water trap is connected with monochloroethane holding tank;
The waste liquid cooling condensation device be connected successively with liquid outlet opening and acid alcohol recovery tower, the described cooling fluid discharge port of waste liquid cooling condensation device is connected with the mother liquor mouth of monochloroethane reaction unit, and the gas discharge mouth of described waste liquid cooling condensation device is connected with the opening for feed of described acid alcohol recovery tower; The ethanol discharge port of described acid alcohol recovery tower is connected with the ethanol opening for feed of monochloroethane reaction unit.
As preferably, also comprise hydrogen chloride gas preparation facilities;
The aqueous phase discharge port of described water trap is connected with the water-in of one-level water absorption unit simultaneously;
The acid solution outlet of described secondary water absorption unit is connected with the water-in of one-level water absorption unit;
The ethanol discharge port of described acid alcohol recovery tower is connected with the ethanol opening for feed of described monochloroethane reaction unit;
The acid solution outlet of described one-level water absorption unit is connected with the water-in of hydrogenchloride concentration unit;
The hydrochloric acid discharge port of described acid alcohol recovery tower and the hydrochloric acid discharge port of hydrogenchloride concentration unit are connected with the opening for feed of described hydrogen chloride gas preparation facilities; The hydrogen chloride gas discharge port of described hydrogen chloride gas preparation facilities is connected with the opening for feed of described monochloroethane reaction unit.
In said apparatus, the opening for feed of monochloroethane reaction unit, hydrogen chloride gas preparation facilities, one-level water absorption unit can be one or more, can need to determine according to working control.
The present invention adopts relative low temperature to react, the generation of by product ether etc. can be reduced, eliminate traditional concentrated acid refining plant, simplify last handling process, and be separated the traditional Alkali absorption method of replacement with the absorption of two-stage water with water after reaction, effectively reduce the quantity discharged of high-salt wastewater, reduce monochloroethane simultaneously and be hydrolyzed the product loss caused, achieve zero generation of by product, replace hydrochloric acid with hydrogen chloride gas during mother liquid recycle simultaneously, effectively reduce energy consumption when wastewater flow rate and mother liquor concentrations, significantly reduce production cost.Therefore, the method be a kind ofly integrate efficient, the synthetic method of clean and economy.
Compared with the existing technology, beneficial effect of the present invention is embodied in: the first, adopts relative low temperature reaction, effectively reduces equipment requirements, improve equipment life; The second, adopt temperature-gradient method reaction, effectively reduce the generation of by product ether etc., compare traditional technology, decrease concentrated acid purifying treatment link, improve product yield, reduce spent acid processing cost; 3rd, replace hydrochloric acid with hydrogen chloride gas during mother liquid recycle, reduce energy consumption during mother liquor concentrations, also reduce wastewater flow rate simultaneously, reduce environmental pollution; 4th, absorb with two-stage water after reaction and be separated the traditional Alkali absorption of replacement with water, decrease the hydrolysis of monochloroethane, decrease the discharge of high-salt wastewater, reduce costs; 5th, be back in reaction after the alcohol of collection and regeneration of hydrochloric acid, meet cleanly production and resources circulation requirement again.
In a word, this synthetic method have equipment requirements low, pollute the advantages such as little and aftertreatment is simple, effectively can reduce energy consumption, save production cost, meet cleanly production and recycling economy development requirement.
Accompanying drawing explanation
Fig. 1 is the schema preparing monochloroethane of the present invention.
Embodiment
Embodiment 1:
If Fig. 1 is the schema preparing monochloroethane in the present embodiment;
First batch of: the technical hydrochloric acid 325kg adding alcohol 107kg and 31% in reactor, after add zinc chloride 600kg, finish rear be slowly warmed up to 80 DEG C insulation 3h, after be warming up to 100 DEG C insulation 3h, be warming up to 110 DEG C of insulation 2h again, when question response pot weight is substantially constant, stopped reaction.About 50 DEG C, buffering is cooled to through one-level successively from reactor gas mixture out, secondary is cooled to 30 DEG C, one-level water absorbs, secondary water absorbs, finished product cooling condensation extremely about 0 DEG C, water trap are separated and obtain finished product monochloroethane, through gas chromatographic detection content 99.5%, weigh and obtain monochloroethane 128kg, yield is 85.3%; Mixed solution after separation through heat up concentrated after for mother liquid recycle, the gas steamed is collected after cooling condensation, the liquid collected is through acid alcohol recovery tower recovered alcohol and hydrochloric acid soln, the alcohol reclaimed is used for assorted pot reaction, and the hydrochloric acid soln of recovery enters hydrogen chloride gas preparation facilities and reacts for assorted pot.15% is greater than when one-level water absorbs the acid waste water concentration produced, when secondary water absorption liquid acid number is greater than 5%, need to change one-level water absorption liquid and secondary water absorption liquid in time, one-level water absorbs and secondary water absorbs the hydrochloric acid that the sour water produced utilizes chlor-alkali hydrochloric acid synthetic furnace synthesis mass percent concentration 30%, and reuse is to hydrogen chloride gas preparation facilities.
Mother liquid recycle: (1) adds 100kg alcohol in reactor, passes into 90kg hydrogen chloride gas after finishing, finish rear be slowly warmed up to 80 DEG C insulation 3h, after be warming up to 100 DEG C insulation 3h, be warming up to 110 DEG C of insulation 2h again, when question response pot weight is substantially constant, stopped reaction.From reactor gas mixture out successively through one-level be cooled to 55 DEG C, surge tank, secondary is cooled to 30 DEG C, one-level water absorbs, secondary water absorbs, finished product cooling condensation to-2 DEG C, water trap is separated and obtains finished product monochloroethane, through gas chromatographic detection content 99.2%, weigh and obtain monochloroethane 120kg, yield is 90.1%; Mixed solution after separation continues to apply mechanically after heating up and concentrating, the gas steamed is collected after cooling condensation, the liquid collected is through acid alcohol recovery tower recovered alcohol and hydrochloric acid soln, and the alcohol of recovery is used for assorted pot reaction, and the hydrochloric acid soln of recovery enters hydrogen chloride gas preparation facilities and reacts for assorted pot.
Comparative example 1
In reactor, add the technical hydrochloric acid 325kg of alcohol 107kg and 31%, after add zinc chloride 600kg, be warming up to after finishing 110 DEG C insulation 5h, when question response pot weight is substantially constant, stopped reaction.About 50 DEG C, buffering is cooled to through one-level successively from reactor gas mixture out, secondary is cooled to 30 DEG C, one-level water absorbs, secondary water absorbs, finished product cooling condensation extremely about 0 DEG C, water trap are separated and obtain finished product monochloroethane, through gas chromatographic detection content 90%, weigh and obtain monochloroethane 120kg, yield is 80%; Mixed solution after separation through heat up concentrated after for mother liquid recycle, the gas steamed is collected after cooling condensation, the liquid collected is through acid alcohol recovery tower recovered alcohol and hydrochloric acid soln, the alcohol reclaimed is used for assorted pot reaction, and the hydrochloric acid soln of recovery enters hydrogen chloride gas preparation facilities and reacts for assorted pot.20% is greater than when one-level water absorbs the acid waste water concentration produced, when secondary water absorption liquid acid number is greater than 5%, one-level water after replacing absorbs and secondary water absorbs the hydrochloric acid that the acidic aqueous solution produced utilizes chlor-alkali hydrochloric acid synthetic furnace synthesis mass percent concentration 30%, and reuse is to hydrogen chloride gas preparation facilities.
Mother liquid recycle: (1) adds 100kg alcohol in reactor, passes into 90kg hydrogen chloride gas after finishing, be warmed up to 110 DEG C of insulation 5h after finishing, reactor weight is substantially constant.From reactor gas mixture out successively through one-level be cooled to 55 DEG C, surge tank, secondary cools 30 DEG C, one-level water absorbs, secondary water absorbs, finished product cooling condensation to-2 DEG C, water trap is separated and obtains finished product monochloroethane, through gas chromatographic detection content 87%, weigh and obtain monochloroethane 123.4kg, yield is 88%; Mixed solution after separation continues to apply mechanically after heating up and concentrating, the gas steamed is collected after cooling condensation, the liquid collected is through acid alcohol recovery tower recovered alcohol and hydrochloric acid soln, and the alcohol of recovery is used for assorted pot reaction, and the hydrochloric acid soln of recovery enters hydrogen chloride gas preparation facilities and reacts for assorted pot.
Comparative example 2
First batch of: the technical hydrochloric acid 325kg adding alcohol 107kg and 31% in reactor, after add zinc chloride 600kg, finish rear be slowly warmed up to 80 DEG C insulation 3h, after be warming up to 100 DEG C insulation 3h, be warming up to 110 DEG C of insulation 2h again, when question response pot weight is substantially constant, stopped reaction.About 50 DEG C, buffering is cooled to through one-level successively from reactor gas mixture out, secondary is cooled to 30 DEG C, the alkali liquor absorption of 660kg15%, finished product cooling condensation extremely about 0 DEG C, water trap are separated and obtain finished product monochloroethane, through gas chromatographic detection content 99.6%, weigh and obtain monochloroethane 124.5kg, yield is 83%.
Mother liquid recycle: (1) adds 100kg alcohol in reactor, passes into 90kg hydrogen chloride gas after finishing, finish rear be slowly warmed up to 80 DEG C insulation 3h, after be warming up to 100 DEG C insulation 3h, be warming up to 110 DEG C of insulation 2h again, when question response pot weight is substantially constant, stopped reaction.From reactor gas mixture out successively through one-level be cooled to 55 DEG C, surge tank, secondary be cooled to 30 DEG C, the alkali liquor absorption of 660kg15%, finished product cooling condensation to-2 DEG C, water trap is separated and obtains finished product monochloroethane, through gas chromatographic detection content 99.4%, weigh and obtain monochloroethane 122kg, yield is 87%.PH=4 ~ 6 after the alkali lye of 15% applies mechanically 4 batches, now need to change alkali lye in time.
Comparative example 3
First batch of: the technical hydrochloric acid 325kg adding alcohol 107kg and 31% in reactor, after add zinc chloride 600kg, finish rear be slowly warmed up to 80 DEG C insulation 3h, after be warming up to 100 DEG C insulation 3h, be warming up to 110 DEG C of insulation 2h again, when question response pot weight is substantially constant, stopped reaction.About 50 DEG C, buffering is cooled to through one-level successively from reactor gas mixture out, secondary is cooled to 30 DEG C, alkali liquor absorption, the 500kg98% vitriol oil of 660kg15% absorb, finished product cooling condensation extremely about 0 DEG C, water trap are separated and obtain finished product monochloroethane, through gas chromatographic detection content 99.9%, weigh and obtain monochloroethane 108kg, yield is 72%.
Mother liquid recycle: (1) adds 100kg alcohol in reactor, passes into 90kg hydrogen chloride gas after finishing, finish rear be slowly warmed up to 80 DEG C insulation 3h, after be warming up to 100 DEG C insulation 3h, be warming up to 110 DEG C of insulation 2h again, when question response pot weight is substantially constant, stopped reaction.From reactor gas mixture out successively through one-level be cooled to 55 DEG C, surge tank, secondary be cooled to 30 DEG C, the alkali liquor absorption of 660kg15%, finished product cooling condensation to-2 DEG C, water trap is separated and obtains finished product monochloroethane, through gas chromatographic detection content 99.8%, weigh and obtain monochloroethane 112.5kg, yield is 75%.PH=4 ~ 6 after the alkali lye of 15% applies mechanically 4 batches, now need to change alkali lye in time; After the vitriol oil applies mechanically 3 batches, massfraction is about 85%, changes during solution milky turbidity.
For research self-control monochloroethane on subsequent intermediates and filter cake with or without impact, outsourcing monochloroethane and self-control monochloroethane synthesis 3-N is adopted in intermediate synthesis, N-diethylamino Acetanilide, the 3-N will obtained again, N-diethylamino Acetanilide is respectively used to the synthesis of 63 DISPERSE Violet 63 93:1, and detailed process is as follows:
Embodiment 2:3-N, the preparation of N-diethylamino Acetanilide: the 3-acetylaminoaniline making beating liquid containing 115g (amount of giving money as a gift) is joined in autoclave, add oxidation 30g, add monochloroethane 115g fast afterwards, after be warming up to 100 DEG C ~ 105 DEG C insulation reaction, after 24 hours, decrease temperature crystalline, washing filtering obtain 3-N, N-diethylamino Acetanilide.
Comparative example 2: according to the method for embodiment 2, replaces outsourcing monochloroethane to participate in reaction with the self-control monochloroethane of equivalent, obtains corresponding 3-N, N-diethylamino Acetanilide.
The preparation of embodiment 3: 63 DISPERSE Violet 63 93:1: the sulfuric acid of 70g nitrosyl sulfuric acid, 15g98% is added in four-hole boiling flask, 2,4-dinitrobenzene-6-chloroanilines and 2,4 dinitro 6 bromo aniline 35g that mass ratio is 10:1 are added under stirring, control temperature is no more than 40 DEG C of reactions, stand-by.By 43g3-N, N-diethylamino Acetanilide adds in the 1000mL beaker containing the 10% sulfuric acid ice aqueous solution (adopting 98% vitriol oil configuration to form), completely reacted diazo liquid is added in beaker, control coupled reaction temperature-5 ~ 5 DEG C, react complete through crystallization, suction filtration and washing, obtained 63 DISPERSE Violet 63 93:1 filter cake.
Comparative example 3: according to the method for embodiment 3, with the 3-N of equivalent self-control monochloroethane synthesis, N-diethylamino Acetanilide replaces the 3-N of outsourcing monochloroethane synthesis, and N-diethylamino Acetanilide participates in coupled reaction, obtains corresponding 63 DISPERSE Violet 63 93:1 filter cake.
To the 3-N with outsourcing monochloroethane and the synthesis of self-control monochloroethane, N-diethylamino Acetanilide carries out determination of quality index, and concrete outcome is as following table 1:
Table 13-N, N-diethylamino Acetanilide quality index
Respectively with the 3-N synthesized by outsourcing monochloroethane and self-control monochloroethane, N-diethylamino Acetanilide synthesis 63 DISPERSE Violet 63 93:1, carry out determination of quality index to the 63 DISPERSE Violet 63 93:1 filter cake of synthesis, concrete outcome is as following table 2:
Table 2 63 DISPERSE Violet 63 93:1 quality index
From table 1 and table 2, the monochloroethane adopting the inventive method to prepare and outsourcing monochloroethane synthesis 3-N, the indices of N-diethylamino Acetanilide and the purple 93:1 of corresponding dye dispersion is basically identical, the present invention simultaneously not only can simplify purifying operation, reduce energy consumption, also can reduce high-salt wastewater and acidic organic wastewater amount, can suitability for industrialized production be carried out.
Claims (10)
1. a process for cleanly preparing for monochloroethane, is characterized in that, comprises the steps:
(1), in first pot reaction, ethanol, hydrochloric acid and catalyzer are joined in monochloroethane reaction unit, 80 ~ 120 DEG C are carried out substitution reaction;
(2) from monochloroethane reaction unit, monochloroethane gas mixture is out separated obtains finished product monochloroethane through one-level cooling, buffering, secondary cooling, the absorption of one-level water, the absorption of secondary water, finished product cooling condensation, water trap successively; The acid number of described one-level water absorption liquid and secondary water absorption liquid is less than or equal to 25%, when in described one-level water absorption liquid and secondary water absorption liquid, the acid number of water is greater than 20%, change fresh water, hydrogen chloride gas reuse for the preparation of hydrogen chloride gas, and is carried out assorted pot reaction to step (1) by the one-level water absorption liquid simultaneously more swapped out and secondary water absorption liquid;
(3) from monochloroethane reaction unit mixed solution out through heat up concentrated after, concentrated solution is back in step (1) as mother liquor and carries out assorted pot reaction as mother liquor, the concentrated gas steamed is collected after cooling condensation, the liquid collected reclaims ethanol and hydrochloric acid soln through acid alcohol recovery tower, the ethanol reuse of reclaiming carries out assorted pot reaction to step (1), hydrogen chloride gas reuse for the preparation of hydrogen chloride gas, and is carried out assorted pot reaction to step (1) by the hydrochloric acid soln reclaimed.
2. the process for cleanly preparing of monochloroethane according to claim 1, is characterized in that, in step (1) reaction process, adopts temperature-gradient method:
First paragraph is warming up to 80 ~ 95 DEG C, reacts 2 ~ 4 hours;
Second segment is warming up to 95 ~ 110 DEG C, and the reaction times is 3 ~ 6 hours;
3rd section is warming up to 110 ~ 120 DEG C, reacts 2 ~ 4 hours.
3. the process for cleanly preparing of monochloroethane according to claim 1, is characterized in that, the acid number controlling one-level water absorption liquid and secondary water absorption liquid is less than or equal to 20%; When one-level water absorption liquid is greater than 15%, secondary water absorption liquid acid number is greater than 5%, change fresh water.
4. the process for cleanly preparing of monochloroethane according to claim 3, it is characterized in that, hydrogenchloride concentration unit the first order absorption liquid more swapped out and secondary absorption liquid is utilized to synthesize the hydrochloric acid of mass percent concentration 30% or more, utilize this hydrochloric acid to prepare hydrogen chloride gas, the hydrogen chloride gas prepared passes into and carry out assorted pot reaction to step (1).
5. the process for cleanly preparing of monochloroethane according to claim 1, is characterized in that, during the reaction of first pot to be mass percent concentration be 25 ~ 35% hydrochloric acid, wherein in ethanol and hydrochloric acid, the mol ratio of hydrogenchloride is 1:1.15 ~ 1.35; The mass percent concentration of catalyzer controls 55% ~ 75%.
6. the process for cleanly preparing of monochloroethane according to claim 1, is characterized in that, the process of assorted pot reaction is:
(1) add the ethanol of set amount, described ethanol is selected from the ethanol of ethanol finished product or recovery;
(2) collect hydrochloric acid soln, first order absorption liquid, secondary absorption liquid, the concentrated hydrochloric acid obtained, to hydrogenchloride concentration unit, joins in hydrogen chloride preparation device by reuse, and the hydrogen chloride gas obtained is passed in the mother liquor after reuse again;
(3) after the hydrogen cloride concentration in mother liquor reaches set(ting)value, stop passing into hydrogenchloride; The ethanol added is 1:1.15 ~ 1.25 with the mol ratio of the hydrogenchloride passed into.
7. the process for cleanly preparing of monochloroethane according to claim 1, is characterized in that, after one-level cooling, the temperature of monochloroethane gas mixture is 50 ~ 60 DEG C; After secondary cooling, the temperature of monochloroethane gas mixture is 20 ~ 40 DEG C, and after finished product cooling condensation, the temperature of monochloroethane mixture is 0 ~ 5 DEG C.
8. the process for cleanly preparing of monochloroethane according to claim 3, it is characterized in that, in step (2) and (3), during the first reuse of secondary absorption liquid absorbs to one-level water, then obtain changing the hydrochloric acid that first order absorption liquid utilizes hydrogenchloride concentration unit synthesis mass percent concentration 30% or more, join in hydrogen chloride preparation device by the hydrochloric acid prepared, the hydrogen chloride gas obtained is passed in the mother liquor after reuse again and carries out assorted pot reaction.
9. a cleaning production apparatus for monochloroethane, comprises the monochloroethane reaction unit with opening for feed, gas discharge mouth and liquid outlet opening, it is characterized in that, also comprise:
The one-level refrigerating unit be connected successively with gas discharge mouth, snubber assembly, secondary refrigerating unit, one-level water absorption unit, secondary water absorption unit, finished product cooling condensation device and water trap, the outlet for product of described water trap is connected with monochloroethane holding tank;
The waste liquid cooling condensation device be connected successively with liquid outlet opening and acid alcohol recovery tower, the described cooling fluid discharge port of waste liquid cooling condensation device is connected with the mother liquor mouth of monochloroethane reaction unit, and the gas discharge mouth of described waste liquid cooling condensation device is connected with the opening for feed of described acid alcohol recovery tower; The ethanol discharge port of described acid alcohol recovery tower is connected with the ethanol opening for feed of monochloroethane reaction unit.
10. the cleaning production apparatus of monochloroethane according to claim 9, is characterized in that, also comprises hydrogenchloride concentration unit and hydrogen chloride gas preparation facilities;
The aqueous phase discharge port of described water trap is connected with the water-in of one-level water absorption unit simultaneously;
The acid solution outlet of described one-level water absorption unit, secondary water absorption unit is connected with the water-in of hydrogenchloride concentration unit;
The ethanol discharge port of described acid alcohol recovery tower is connected with the ethanol opening for feed of described monochloroethane reaction unit; The hydrochloric acid discharge port of described acid alcohol recovery tower and the hydrochloric acid discharge port of hydrogenchloride concentration unit are connected with the hydrochloric acid opening for feed of described hydrogen chloride gas preparation facilities; The hydrogen chloride gas discharge port of described hydrogen chloride gas preparation facilities is connected with the hydrogenchloride opening for feed of described monochloroethane reaction unit.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106831315A (en) * | 2017-01-18 | 2017-06-13 | 浙江迪邦化工有限公司 | A kind of continuous production method of chloroethanes |
| CN112058859A (en) * | 2020-08-19 | 2020-12-11 | 浙江巨化技术中心有限公司 | High-waste treatment device and method for chlorohydrocarbon |
| CN112300001A (en) * | 2020-11-10 | 2021-02-02 | 宁夏瑞泰科技股份有限公司 | Production method for co-production of ethyl chloroformate and ethyl chloride |
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| CN102850178A (en) * | 2012-08-24 | 2013-01-02 | 江苏振方医药化工有限公司 | Method for synthesizing ethyl chloride by using gas phase hydrogen chloride and ethanol |
| CN103044187A (en) * | 2013-01-17 | 2013-04-17 | 江苏银珠化工集团有限公司 | Method and system for producing ethyl chloride |
| CN103351274A (en) * | 2013-08-06 | 2013-10-16 | 河南清水源科技股份有限公司 | Low-temperature low-pressure gas-liquid-phase monochloromethane synthesis process |
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| CN102850178A (en) * | 2012-08-24 | 2013-01-02 | 江苏振方医药化工有限公司 | Method for synthesizing ethyl chloride by using gas phase hydrogen chloride and ethanol |
| CN103044187A (en) * | 2013-01-17 | 2013-04-17 | 江苏银珠化工集团有限公司 | Method and system for producing ethyl chloride |
| CN103351274A (en) * | 2013-08-06 | 2013-10-16 | 河南清水源科技股份有限公司 | Low-temperature low-pressure gas-liquid-phase monochloromethane synthesis process |
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| CN106831315A (en) * | 2017-01-18 | 2017-06-13 | 浙江迪邦化工有限公司 | A kind of continuous production method of chloroethanes |
| CN106831315B (en) * | 2017-01-18 | 2020-02-07 | 浙江迪邦化工有限公司 | Continuous production method of chloroethane |
| CN112058859A (en) * | 2020-08-19 | 2020-12-11 | 浙江巨化技术中心有限公司 | High-waste treatment device and method for chlorohydrocarbon |
| CN112300001A (en) * | 2020-11-10 | 2021-02-02 | 宁夏瑞泰科技股份有限公司 | Production method for co-production of ethyl chloroformate and ethyl chloride |
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